Treatment of fermentation products



' Patented Apr. 10, 1951 TREATMENT OF FERMENTATION PRODUCTS Joseph Bernard Edmondsj'B'altimore," Md.

. NorDrawing. :ApplicationsApril 2,1948, .SerialNo. 18,721

*3 Claims. (Cl. 99-405) This; invention relates'to an improved process for quantitative precipitation of excess tartr'ates from, juices .and wines, particularly grape juices aridw'ines, at normal temperatures by means of a soluble compound of calcium.

Prior ,processes involving the removal of excess tartrates oi .argols .from Wines or the like generally necessitate long periods of storage at low tempera'turescr shorter periods with refrigeration .atfreezing temperatures .of 1829 degrees F. .andfiltaltion o'f the ibitartrates at 32-35 degreesiRIto .prevent the precipitate from redissolving, since the acid tartrate' increases in solubility with'sa-risein temperature. Other methods-employed'tinithelremoval oftheiexcessrtartrates'involve the introduction of precipitating x'ag'ents and particularly calcium salts, both inorganic and organic. However,"these processes ar undesirable since theyaITect-the quality ofthe product, as well as change-the basic .composition so as to violate the Federal lawson the subject. Other methodsof preparation involve the addition of acids which yield toxic products, aor the zeolitic treatment of juices, or oxidation of the frozen grape juices to "induce precipitation, "but none-"of thesehave proved xto be.entirely satisfactory.

It has now-'beenzdiscovered lthat! any calculated amount of potassium bitartrate can be quantitatively precipitated .from grapejuiceor .wine by the addition of a prepared compound of calcium withoutiafiecting the color,:.;fiavor, or basic composition of the product so treated. A stable product.iree of excessitartratesis obtained thereby. .In the present method, long period of stor age atclow temperatures, or refrigeration ofthe treateidiuieeor wine'zisavoided.

"In "order to insure complete precipitation "of the .tartrates, tit is necessary to :supply enough calciumions to precipitate the.desired quantity'of potassium bitartrates as WeILasraiSe thepI-Lof the solution approximately one .unit to insure best results. While it is simple to determine the calcium ions needed to precipitate the tartrates plus an excess -of-the mixture to raise thepH, it has been discovered'that an equivalent weight of the mixture will react with'the same 'w'eight'of the potassium bitartrate, disclosing a complete exchange or the'ca'lcium and potassium ions, and having at the same time suflicient excess of the mixture .to..raise..the pH value of the-treated product thus fobviating thenecessity -for tedious calculations. 'This' definite.reactioniistapparently controlled "by the 33H -of the "compound 1 and its limited solubility.

obj ect of the inventionis to produce anexcesstartra'tairee :product without changing the color iiavor, or-=basic composition in any manner.

Another object ofQtheiinvention is toobtain rapid results without the necessity for'long periods of storage oitrefrigeration. to the undesired tartrates contained .in .the grape juices .or wines.

futher object,.of..the'iiriveritionis to eliminate the .necessity .for carefully .calctila'ting the amounts tof precipitating -agen't needed to .fii ciently=oarry-outtheprocess.

:A stillfurther objectpf-theiinverition is to provide .a compound that wilLnotincreaseLin.solubility with irisesinmtemperature andlitssolubilityL not-affected by the addition to .w'inesor. grape Jl-llCeS.

:And yet a .further :object .of the inventioniis to provideeanrinexpensive .methodpf rapidly removing-tartariceacid=andltartrates from the.materials topeltreated.

.The, fpreparationeoflthis compound requires that the calcium oxide or hydrate :be neutralizedwith fruit acids -such1as citric or malic acid .to :result in:awmixturevhavingan alkalinityiof 1.8.

.The.ingredients"employedare:

.( l) Malic acidror. citric acid (:2) vCaloium 1 oxide .(dree from -iron tan'd heavy *metals -.orcalcium hydroxidetasabovekusffl.

iiExamplesiopthe method 'of preparation:

Galcium mxirle 1.129 131 Suffic'ierit Water to wet the above mixture was added, after which it lwas mixed and agitated until .all lumps were removed .and theresulting slurry showed .a :p'H .o'f"7'.'88$2. The' heat- ,of "reaction produced ..a 'Ifine vvliitegpowderhaiiing 'a solubility .of 0Aigm.:in100.c. c...of.cold water and a solubility sof 0.5 .gm. :in :"C. -.c. of -hot water,

'whichsolubility. is nottincreased-lby the addition offgnapeijui'oe or wine.

Calciumthydroxide-.. i1f66 Q1168 The above substances were wetted and mixed in the manner of Example I to produce a fine white powder similar to that obtained in the preceding illustration.

The proportions of materials used are very definite and are of a limited range in order to insure the proper pH and solubility of the resulting compound.

In order to treat grape juice or fermented grape wine with the mixture prepared in Examples I and II, it is necessary to determine the amount of potassium bitartrate and the pH value of the product to be treated. It has been found that in normal practice grape juice requires the removal of approximately 0.20-0.30 percent of potassium bitartrate, and fermented wine requires the removal of 0.10-0.20 percent in order to produce a stable product.

The following examples illustrate the practical use of the invention, although it is to be understood that they can be varied to meet other conditions and are for the purposes of illustration only and are not limited to the specific details disclosed therein.

EXANIPLE III 100 gallons of freshly pressed grape juice containing potassium bitartrate calculated as 1.00 percent total tartaric acid, with a pH value of 2.5 requires the removal of 0.3 percent, or 2.5 pounds of potassium bitartrate to produce a juice free from excess tartrates. To precipitate this amount of potassium bitartrate, and to raise the pH value to 3.5, it requires the same amount of the mixture as prepared in the above examples, or 2.5 pounds per 100 gallons of the juice. After adding the mixture, the juice is heated to 120-130 degrees F., mixed thoroughly, and then allowed to stand at normal room temperatures for approximately 15 days to allow precipitation of the desired amount of potassium bitartrate as insoluble calcium tartrate.

Prolonged agitation without heating immediately after addition of the mixture will speed up the reaction, and insure complete mixing. The crystallization will occur immediately, and the crystals willsettle in the bottom of the vessel. After the reaction is completed, the juice is then drawn or racked off, free from the insoluble calcium tartrate crystals. The storage of the grape juice during the eriod of treatment can either be pasteurized and sealed in closed containers, or refrigerated to prevent fermentation, without interference with the efliciency of the above process in removing the desired amount of potassium bitartrate.

The resultant juice will show a reduction of cream of tartar, total tartaric acid, and ash.

EXAMPLE IV 100 gallons of fermented grape wine containing potassium bitartrate calculated as 0.55 percent total tartaric acid, and with a pH of 3.5, was used. It is necessary to remove 0.1 percent or 0.84 pound of potassium bitartrate in this sample in order to produce a stable product and this requires 0.84 pound of the alkaline mixture to precipitate the equivalent amount of potassium bitartrate. After addition of the calcium, the wine is then heated to 120-130 degrees F., or with a portion of the wine, and then the entire quantity is mixed thoroughly. Prolonged agitation or pumping over without heat also speeds up the reaction and insures complete: mixing. The wine is then permitted to remain at normal temperatures, that is, 65-75 degrees F. for approximately 15 days in order to precipitate the desired quantity of potassium bitartrate as insoluble calcium tartrate. This is then filtered out by ordinary filtration methods at normal temperatures.

Any Wine can be treated immediately with the above mentioned salts and the precipitates formed will be allowed to settle throughout the usual period of cellar treatment, or a finished wine can be treated and allowed to remain in storage until the precipitation is complete. This treatment will not interfere with the normal operations carried out in the manufacture of wines. The resultant wine after treatment will show a reduction in the amount or" cream of tartar, total acids as tartaric, and ash, and is exactly as is usually found in the normal practice of long periods of storage at low temperatures, or refrigeration at sub-freezing temperatures for shorter periods.

A number of fine wines and grape juices were treated by the method of this invention and the results obtained compared favorably with similar wines that were untreated or treated by the conventional refrigeration method. Below are a number of tables disclosing the results of the analyses, and it is to be noted that in every instance there was a substantial reduction in the cream of tartar contents, and, in addition, in general, there was a material reduction in the total acids and total ash of the materials tested.

ANALYSES OF WINE AND GRAPE JUICE TREATED WITH 'AHE SOLUBLE CALCIUM COMPOUND DISCLOSED sovs Table I .-New York State dry red wine Untreated Treated Refrigerated Total A rid s .457% Total Ash. Alkalinity of Solu- .204% .180% 164%. 19.0 cc./l00 10.5 cc./100.-- 12.0 cc./100. ble Ash. Alkalinity of Insol- 16.0 (KL/100...-

15.5 cc. 17.0 cc. 100. uble Ash. I I

Cream of Tartan- 36%- .20

Phosphorus Pent- .02l0%.

oxide.

Table lL- -Dry'white wine Untreated Treated Refrigerated Total Acids Total Ash 292% Alkalinity of Solu- 20.0 cc./l00.--

ble Ash.

Alkalinity of Insol- 21.0 ec./l00.

uble Ash.

Cream of Tartan--. Phosphorus Pentoxi e. Calcium 0xide 12.0 cc./l00. 13.5 (KL/100.

.Table III .COnc01'cZ grape wine Wine Treated After Fermentation Juice Before Fermentation Treated Untreated Treated Refrigerated (Settled 2 Months) Total Acids 660% .517%. 537%. Total Ash 400%. .366% .4l8%. Alkalinity of Soluble Ash 21.0 cc./100-. 19.0 cc./100. 22.0 cc./l00. Alkalinity of Insoluble Ash 14.5 cc./lC0- 15.0 cc./l00 24.0 cc./l00. Cream of Tartar 36% .41 Calcium Oxide .014l% .0147% .0l40%. .0l49%. Phosphorus Pentoxid .056%. .0578% .O548%- The advantage of the instant process is that in the raising of the pH of the products treated, the speed of the reaction is increased and results in eificient precipitation of the total acids. The solubility of the calcium mixture is not increased when added to the grape juice or the wine, such results being usually the case in previously used precipitating agents, causing the calcium to go into solution and falling within the prohibitions of the Federal laws governing the production of these products. There is absolutely no change in the final product other than that which is normally produced in the conventional aging of grape products.

Although there has been described a preferred manner of carrying out the process, it is to be understood that the application is not limited to the precise method disclosed except as may be required by the scope of the following claims.

Having described the invention, What is claimed as new is:

1. A process for removing excess tartrates from grape extracts comprising adding to a predetermined quantity of potassium bitartrate a substance having a pH of 7.8-8.2 in aqueous slurry thereof consisting of a compound selected from the group consisting of calcium oxide and calcium hydroxide admixed with a salt selected from the group consisting of calcium malate and calcium citrate, heating the solution, agitating thoroughly, and reducing the temperature of the solution to precipitate calcium tartrate, said substance being added in an amount equal to the weight of potassium bitartrate to be removed, said substance raising the DH of the clarified extract one unit.

2. The process of claim 1 wherein the solution is heated to -130 F. and the temperature is reduced to room temperature.

3. The process of claim 2 and the step of removing the precipitated calcium tartrate.

JOSEPH BERNARD EDMONDS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,427,903 Johnston Sept. 5, 1922 1,491,390 Glaeser Apr. 22, 1924 1,876,366 Ungnade Sept. 2, 1932 1,915,273 Eoif June 27, 1933 2,002,842 Torigian May 28, 1935 

1. A PROCESS FOR REMOVING EXCESS TARTRATES FROM GRAPE EXTRACTS COMPRISING ADDING TO A PREDETERMINED QUANTITY OF POTASSIUM BITARTRATE A SUBSTANCE HAVING A PH OF 7.8-8.2 IN AQUEOUS SLURRY THEREOF CONSISTING OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF CALCIUM OXIDE AND CALCIUM HYDROXIDE ADMIXED WITH A SALT SELECTED FROM THE GROUP CONSISTING OF CALCIUM MALATE AND CALCIUM CITRATE, HEATING THE SOLUTION, AGITATING THOROUGHLY, AND REDUCING THE TEMPERATURE OF THE SOLUTION TO PRECIPITATE CALCIUM TARTRATE, SAID SUBSTANCE BEING ADDED IN AN AMOUNT EQUAL TO THE WEIGHT OF POTASSIUM BITARTRATE TO BE REMOVED, SAID SUBSTANCE RAISING THE PH OF THE CLARIFIED EXTRACT ONE UNIT. 